Novel dyeing effects



Patented Sepb'28, 1943 .UNl'l ED- STATES PATENT OFFICE a... n. $3.235.- EVZFHEZTL A1... 1..

Honk, Philadelphia, Pa.,

Philadelphia Haas Company,

assignors to Riihm &

No Application-March 12, 1941, Serial N0. 382,940

8 Claims.

This invention relates to a method for producing novel coloring eflects in textile fabrics containing cellulosic fibers or regenerated cel-.

lulosic fibers. In particular, this invention deals with creating effects in the drains of fabrics containing cotton, linen, ramie, other cellulosic fibers or regenerated cellulosic fib'ersby altering the capacity for dyes of at least a part of said fibersby reaction with a quarter-nary ammonium compound having as an N-substituent at least one The quaternary ammonium compounds which are useful in this invention have the general formula 1 B1 RI ROCHr N esses have required complicated procedures, ex-

cessively long periods of treatment, or techniques whichare scarcely practical in the averag textile mill. As -a result of such processes, fabrics have been unduly tendered at times and the fabrics jso treated have been seriously changed in their physical appearance and properties. Such iii..-

advantages are avoided by the method herein described for altering the susceptibility of cellulosic fibers to dyestuii's.

In accordance with the present invention decorative and novel effects are obtained in textile fabric containing cellulosic fibers by treating at least part of the cellulosic material making up the fabric with a quaternary ammonium com pound having at least one oxymethyl group having a substituent of 7 to 14 carbon atoms, heating the treated cellulosic material to cause a reaction between it and the said salt, and subsequently applying a dye to the treated and heated material; When the dye applied is one which is normally susbtantive to cotton, the cellulosic material exhibits a reserve effect and is but slightly colored. 0n the other hand, the treated and heated material accepts dyes of the acetate type.

If a cotton fabric is woven in part with untreated, normal yarns and in part wi h y ns which have been treated and heated as described, patterns are obtained when the cloth is dyed with a single dye. The treated and untreated fibers or yams difl'er in color, intensity of color or shade. Novel efl'ects may also be obtained by printing celluloslc fabrics with pastes containing 'a quaternary ammonium compound having. an

oxymethyl group with asubstituent of 7 to 14 carbon atoms. heating the printed fabric to cause a reaction between fabric andsaid compound, and then dyeing the fabric to give patterns.

Novel effects. are also obtained in cross dyeing.

wherein R is an aliphatic, cycloaliphatic, or an aralkyl group having 7 to 14 carbon atoms, X is an anion, and R1, R2, and Rs are organic groups selected to satisfy three valences of the nitrogen from at least one member of the class consisting of trivalent unsaturated hydrocarbon chains which jointly with the nitrogen form a heterocycle, divalent saturated aliphatic chains which jointly with the nitrogen form a heterocycle and monovalent cycloaliphatlc, araliphatic, and aliphatic groups.

Suitable groups for R include n-octyl, isooctyl,c,, ;y-tetramethyl butyl, decyl, undecenyl, dodecyl, hydrocarbon groups from commercial cuts of alcohols having 7 to 14 carbon atoms, ob-

tained, for example from hydrogenated fatty glycerides, or from the alcohols of he methanol catalytic synthesis, methyl cyc ohexyl, cyclohexylcyclohexyl, butylcyclohexyl, benzyl, methyl benzyl, butyl benzyl, etc. Typical groups occurring as X are the-chloride, bromide, iodide, formate, acetate, sulfate, ethyl sulfate, hydroxide, etc. groups. While the halide salts are most readily prepared, it is possible through the hydroxide to form salts with any acid, whether strong or weak, organic or inorganic. The nature of R1, R2, and R; may be widely varied. When the three groups are taken as a trivalent radical, they constitute an unsaturated hydrocarbon chain as is found in pyridine, quinoline, picoline, or the like. When two of the groups together represent-a divalent saturated aliphatic radical, this radical forms with the nitrogen a heterocycle such as occurs in piperidine, morpholine, pyrro'lidine, or the like. With such a divalentgroup there is, of

-or R3 represent monovalent groups, they may represent aliphatic, cycloaliphatic, or araliphatic groups. Typical aliphatic groups include, not only saturated and unsaturated open chain hydrocarbons but also aliphatic groups carrying such functional groups as hydroxyl, halogen, amide, nitrile, ester, ether, aldehyde, ketone,

amino, etc. Typical araliphatic groups include benzyl, methylbeny pnenoiwet y ethoxyphenoxyethyl, etc., while typical of the methyl phenoxyethoxyethyl,

cycloaliphatic groups are the cyclohexyl and methyl cyclohexyl radicals.

Some of the types of compounds which have been found useful in this application of quaternary ammonium salts are as follows:

CH: CHzCcHs CsHnOCHa-N H000 CHzCsHa CH: on,

CB ISCH(CHI)O:CHi-l\ clnisol :11:

on cm cu: cruc H CH OCH on on 9 2 l I I; I-

Hr-Ca r H CH: Ciz uOCHr- C CHrCeHs CH; CH:

CnHzs0CHri C CHQCH=CH 01H: CzHi CnHzsOCHr- Br CzHsOH CH: CH:

CioHiiOCHF CH CHr-&CH:

CHI

CnHnOCHr-N C( CHzCH(CHS) CHO I OH: CH: CAHICH (C:H$)C2HACH (CHQH) 0112- N CH:

C CH:-(BCH2N (C2115):

CiHaCslLCHro CH7- CHQCHIBI 01 1: CnHnOCHz- ,Br .cmcmocmcmomm on. on,

CgHnOCHr o cmcnlcoocln.

CuHuCHGJ Ha) O CH:

CBHIKO on,

Although quaternary ammonium compounds having oxymethyl groups with 'substituents of 7 to 14 carbon atoms are generally suitable for the purposes of this invention, those compounds having such substituents with 10to 12 carbon atoms v are the most efiective.

' ,oi cellulosic materials for In using the quaternary ammonium compounds having an oxymethyl group to alter the capacity dyes. it is necessary to use fairly concentrated solutions thereof, a concentration of about 10% or more required. The range of 10% to 25% is preferred. The quaternary compound may be dissolved in water, an organic solvent such as ethyl alcohol or aceton or in a mixture of solvent and water. The solution may be applied to fiber, yarn, or fabric by sprayin spreading, immersing, printing, or other suitable mode of application. Excess solution may be removed by squeezing, centrifuging. vacuum extracting, or equivalent procedure. The impregnated material is dried and baked at a temperature between about C. and about C. The lower temperature is determined by that atwhich the desired reaction is effected. The permissible upper temperature must be below that at which scorching of fabric would occur with regard to the particular cellulosic material or fabric being treated and the time required to efiect the reaction. Following the reaction it is often desirable to wash the treated material to remove unreacted quaternary compound and reaction products remaining from combining the long chain oxymethyl group with the cellulose. The treated material is subsequently subjected to the action of a dye bath according to any of the usual procedures. If the treated cellulosic materials are in the form of fibers or yarns, they are usually, but not necessarily, made into cloth before the dyeing step. Where printing is involved or in cases where cellulosic yarns are woven, or knitted with other types of fibers, the treating may, of course, be

being usually against such dyes as direct acetate dyes, an increased affinity is exhibited.

The following examples further describe the invention and give illustrative details.

EXAMPLE .1

A skein of cotton yarn was immersed in a aqueous solution of dodecyloxymethyl butyloxymethyl dimethyi ammonium chloride, dried at room temperature and heated in an oven at 130 C. for 30 minutes. rinsed in water, and dyed for 30 minutes at 100 C., in a bath containing 1% Diazine Black OB. Diazine Black OB is listed in the Yearbook of the American Association of Textile Chemists and Colorists as belonging to Foreign Prototype 147. The skein so treated was only lightly colored. A second skein of cotton yarn which was not so immersed in the aqueous solution but which was subjected to the same dyeing bath for the same period of time and at the same temperature was dyed a deep black.

Another skein of cotton yarn was immersed in a aqueous solution of the same quarternary ammoniunr compound and treated as above. This skein showed even greater resistance to dyeing with Diazine Black OB under the same conditions of time, temperature and concentration.

after dried for ten minutes in an oven at 130 C., and then heated for ten minutes in an oven at 150 C. After the heat treatment the cloth was washed with a soap solution, rinsed in water several times. and dyed for minutes at 100 C.

in a bath containing 1% Diazine Black OB. The

resulting cloth was a light, pearl gray.

A piece of cotton sheeting, not treated with the quaternary ammonium salt but dyed in the same bath for the same length of time and at the same temperature, became a rich black in color.

In the same way pieces of the original sheeting and pieces of the shooting impregnated and heated with octyloxymethyl benzyloxymethyl di methyl ammonium chloride were dyed with Benzofast Scarlet 4138A (Color Index No. 327) and with Pontainine' Sky-blue (EB/(Color Index No. 518). The original fabric, untreated with a .quaternary compound, became deep red and royal blue in the two dye baths respectively,

' while the treated pieces were only lightly tinted.

EXAMPLE 3 Kier-boiled and bleached percale was padded through a 20% aqueous solution of dodecyloxymethyl ethoxyethyl dimethyl ammonium chlo-.

parts of sodium hydrosulfite, 10 parts of a 20% aqueous sodium hydroxide solution, and 100 partsoi water by heating the mixture at 70 C. until reduction was complete, and then diluting with 200 parts of boiled water. Pieces of both treated and original fabric were padded through this solution, thereafter treated inan oxidizing bath,- and dried. The original untreated fabric was a full blue, while the treated fabric acquired only a light shade.

12) Pieces of original percale and treated percale were dyed for one hour in a bath at 70C., containing 5 parts of SRA Orange III. an acetate dye, 0.5 part of soap, and 200 parts of water. The original fabric held only a trace of dye while the treated fabric acquired a. deep, full color.

A piece of fabric composed of cellulose acetate was also dyed in the SBA Orange III bath. It became bright red.

(c) Other pieces of original and treated fabrics were steeped for one-half hour at 100 C.. in a bath composed of 5 parts of Calcogene Dark Brown N, 5 parts of sodium sulfide and 200 parts of water. The treated piece retained very little of the dye while the control wa a black-brown.

EXAMPLE 4 An all-spun rayon fabric was padded through a warm 15% solution of octyloxymethyl butyioxymethyl morpholinium chloride, dried, heated for 20 minutes in an oven at 150 C., and there after laundered in hot soap solution, rinsed, and entered in a bath containing 1% of Diazine Black OB, held between and C. The treated fabric took up very little dye, while a piece of the fabric, subjected to the same dye bath under the same conditions but which had not been preliminarily treated, became black.

EXAMPLE 5 (a) A piece of spun rayon fabric was impreg- 'nated with a 20% aqueous solution of capryloxymethyl dimethyl benzyi ammonium hydroxide, dried at room temperature, heated in an oven at .30 C. for one-half hour, and washed. It was then entered into a dye bath containing Benzefast Scarlet 4138A and treated for one-half hour at 100 C. Practically no dye was taken up by the fabric. whereas a piece of the original fabric in the dye bath became a brilliant red.

(1)) A rayon taffeta was padded through a solution containing 20% of capryloxymethyl dimethyl benzyl ammonium hydroxide, dried at low temperature, heated in oven at 140 C. for one-half hour, and washed. It was then treated in a bath containing SRA Orange III, a celanese dye, and treated for an hour at 70 C. A deep orangebrown color was imparted to the treated fabric whereas an untreated'piece of the original fabric retained very little of the dye.

(c) A piece of spun viscose rayon fabric was treated in a 10% aqueous solution of capryloxymethyl dimethyl benzyl ammonium hydroxide, dried at low temperature, heated in an oven at C. for one-half hour, and washed. It was then treated in a bath of SRA Orange III for one hour at 70 C. An orange-brown color was imparted to the fabric and the color was well retained.

The alteration of the dyeing properties of regenerated cellulose is most marked when'quaternary ammonium hydroxides are used or the treating solution contains both hydroxide and salt forms. 0n the other hand, cotton is most effectively treated in this process with the salts.

By generally similar procedures the effects were demonstrated of treating different ceilulosic materials with a variety of dyes. This work is summarized in the following table, in the columns of which are shown the nature of quaternary compound used, its com-.ontratiori: the fabric to which it was applied, the treatment of the impregnated fabric, the dye applied to the 20 20 20 20 20 20 Do 20 Dodecyloxymethyl benzyloxymethyl dimethyl ammonium chloride. Dodecyloxymethyl methallyloxymethyl dimethyl ammonium chloride. Dogecytlioxymethyl butoxymethyl piperidinium 20 c on e. Diisobutylphenoxycthoxyethyl octyloxymethyl 20 dimethyl ammonium chloride.

' Dodgcyloxymethyl pyridinium chloride 20 20 Do. 20 Do. 20 Bcnzylo dimethyl benzyl ammonium 20 chloride.

treated fabric, and the resulting color. In all cases it will be noted the treated fabric responded differently from the original fabric.

It should be noted that the differential dyeing effects are due to an actual chemical modification of part of the cellulosic material, the altera- TABLE I Summaryv of treating fabrics with various 'solts and dyeing Compound Concn. Fabric Per cent Dodecyloxymethyl butoxymethyl dimethyl 20 aubmonium chloride.

Dodecyloxymethyl dimethyl benzyl ammoniumchloride.

Do Dodecyloxymethyl triethyl ammonium chloride. Decyloxymethyl dibenzyl methyl ammonium chloride. Tetrad cyloxymethyl trimethyl ammonium chloride. 2-othylhexyloxymethyl diethyl hydroxyethyl ammonium chloride. Decyloxymcthyl Z-hydroxypropyl dimethyl ammonium chloride. -Dodec,vloxymethyl dimethyl cyclohexyl ammonium chloride.

Dodecyloxymethyl-3-dimethylnmino-2-hydroxy- 20 do propyl dimethyl ammonium chloride.

Dodecyloxymethyl 2-hydroxycthyl morpholin- 20 do ium chloride.

Dodecyloxymethyl 2-formylpro'pyl dimethyl 20 do ammonium chloride.

Dodeeyloxyrnethyl 2-carbomethoxypropyi di- 20 ...do

methyl ammonium chloride.

Dodecyloxymethyl Z-hydroxyoctyl dimethyl. 20 do ammonium chloride.

Dodecyloxymethyl 3-phenylpropinyl-3 dimethyl 20 do ammonium chloride.

Heated Dye used hr. 130 (3..-. Benzo-fast Smrlct 413511.-.. V. lt. pink.

- .do do .Do. 8min. 150 do Pale pink. V hr. C Pontamine Diazo Black Lt. bluegray, 95 hr. C SBA Orange 111 Deep orangebrown. d0 Pontamine Skyblue 6B. Pale blue.

do Calcogene Dark Brown N... Light brown. 5 hr. C Tetrabromo-indigo Light blue. hr. 130 0.--. Pontamine Diazo Black. Medium gray.

do do Pale gray.

do do Light grey.

do .do Medium grey.

Benzo-iast Scarlet 4138A- V. plojlc pink.-. o o. SRA Orange III Med. orange-brown.

. Pontaminc Diazo Blac V. pale gray. SBA Orange III Med. orange-brown.

Dark brown.

Benzo-fast Scarlet 4BSA Pale pink. f." fi f ffff f f:31:? itt? Light gray.

Pale gray.

. do do Do.

do do Do.

do do Med. lt. gray.

.do do Pale gray.

do do Med. pale gray.

do do Pale gray.

EXAMPLE 6 A solution containing about 12% of dodecyloxymethyl pyridinium chloride and 1% of sodium acetate was rubbed through a silk stencil placed over a piece of percale, the stencil permitting 50 transfer of the solution to the percale in local areas. The cloth was then heated for one-half hour at 130 C., washed in soap and water, and placed in a 1% solution of Pontamine Sky-blue 6B for one-half hour at 95100 C. A design was thus developed inthe percale, the treated areas being but lightly tinted'while the untreated areas were a deep blue.

For effecting a change in the dyeing properties of cellulose and regenerated cellulose a solution printing methods anddesigns developed on subsequent heating and dyeing. Decorative effects are also obtained by cross dyeing.

tion involving primarily the surface. The operation of the oxymethyl quaternary compounds in the manner here described is different than that with the usual quaternary salts which have been added to dye baths or used in after-treatments to fix certain dyes on various fibers. In these cases thequaternary salts form complexes with.

the dyes.

In the application of the oxymethyl quaternary ammonium compounds to alter the susceptibility of cellulosic materials to dyes, there may be used in the impregnating solutions salts of weak acids and strong bases, such as sodium acetate, sodium phosphate or the like, or saltsof strong acids and weak bases, such as ammonium chloride. These salts may serve as buffers or as catalysts, but are not essential for the successful performance of the process. There may also be added to aqueous solutions an organic solvent to improve solubility and to decrease the viscosity of the solutions.

The nature of the process is such that it may be practised with standard textileequipment without damage thereto and without harm to the fabrics. Results are highly satisfactory and are uniformly and reproducibly obtained We claim:

1. A method of producing novel coloring effects in a textile fabric containing fibers selected from the class consisting of cellulose and regenerated cellulose fibers by altering the capacity for dyes tion containing at least of at least part of said fibers by increasing affinity thereof for acetate dyes and decreasing afiinity thereof for direct dyes, which comprises impregnating at least part of said fibers with a solution containing about 10% to about 25% of a compound of the formula I R|\ /R2 :ao CH2;

the group consisting of aliphatic a'ndcy'cloaliphatic hydrocarbon groups and aralkyl groups,

X is an anion, and R1, R2 and Rs are organic groups selected to satisfy three valences of the 1 10 wherein R is a group which contains 7 to 14 .carbon atoms and is selected from a member of 7 thereof for direct dyes, which comprises impreg nitrogen atom from at least one member of the class consisting of trivalent unsaturated hydrocarbon chains which jointly with-the nitrogen form a heterocycle, divalent saturated aliphatic chains which jointly with the nitrogen form a thereof for direct dyes, which comprises impregnating at least part of said fibers with a soluof a compound of th formula R1\ /R:

wherein R is a group which contains '7 to 14 carbon atoms and is selected from a member of the group consisting of aliphatic and cycloaliphatic hydrocarbon groups and aralkyl groups, X is an anion, and R1, R2 and R3 are organic groups selected to satisfy three valences ofthe nitrogen atom from at least one member of the class consisting of trivalent unsaturated hydrocarbon chains which jointly with the nitrogen form a heterocycle, divalent saturated aliphatic chains which jointly with the nitrogen form a heterocycle, and monovalent cycloaliphatic, araliphatic, and aliphatic groups, heating the impregnated fibers to a temperature between about 100 C. and

the temperature at which scorching would occur, and subsequently subjecting fabric containing the treated fibers to the action of a dye.

14 carbon atoms and X is an anion, heating the impregnated fibers to a temperature between about 100 C. and the temperature at which scorching would occur, and subsequently subjecting fabric containing the treated fibers to the action of a ye.

4. A method of producing novel coloring effects in a textile fabric containing fibers selected from the class consisting of cellulose and regenerated cellulose by altering the capacity for dyes of at least part of said fibers by'increas'ing afiinity thereof for acetate dyes and decreasing aflinity nating at least part of said fibers with a solution containing about 10% to about 25% of dodecyl oxymethyl pyridinium chloride, heating the 1mpregnated fibers to a temperature between about 100 C. and the temperature at which scorching would occur, and subsequently subjecting fabric containing the treated fibers to the action of a 5. A method of producing novel coloring efiects in a textile fabric containing fibers selected from the class consisting of cellulose and regenerated cellulose by altering the capacity for dyes of at least part of said fibers by increasing aflinity thereof for acetate dyes and decreasing aiiinity thereof for direct dyes, which comprises impregnating at least part of said fibers with a solution containing about 10% to. about 25% 'of a compound of the formula wherein R is selected from a member of the class consisting of aliphatic and cycloaliphatic hydrocarbon groups and aralkyl groups containing 7 to 14. carbon atoms, X is ananion, R1 and R:

are lower alkyl groups, and R3 is an aralkyl group, heating the impregnated fibers to a temperature between about'lOO" C.- and the temperature at which scorching would occur, and subsequently subjecting fabric containing the treated fibers to the action of a dye.

6. A method of producing novel coloring effects in a textile fabric containing fibers selected from the class consisting-of cellulose and regenerated cellulose by altering the capacity for dyes of at least part of said fibers by increasing" aflinity thereof for acetate dyes and decreasingafiinity thereof for direct dyes, which comprises impregnating at least part of said fibers with a solution containing about 10% to about 25% of 'dodecyloxymethyl benzyl dimethyl ammonium chloride, heating the impregnated fibers to a tem- 3. A method of producing novel coloring efiects in a textile fabric containing fibers selected from the class consisting of cellulose and regenerated 'cellulose by altering the capacity for dyes of at least part of said fibers by increasing afiinity thereof for acetate dyes and decreasing afiinity thereof for direct dyes, which comprises impreg nating at least part of said fibers with a solution containing about 10% to about 25% one compound of the formula V wherein R is selected from a member of the class consisting of aliphatic and cycloaliphatic hydrocarbon groups and aralkyl groups containing 7 to thereof for direct dyes, which comprises impreghating at least part of said fibers with a solution containing about 10% to about 25% of a compound of the formula R0 CHr N wherein R is a group which contains 7 to 14 carbon atoms and is selected from a member of the group consisting of aliphatic and cycloaliphatic hydrocarbon groups and aralkyl groups, and R1,

R2, and R3 are organic groups selected to satisfy three valences of the nitrogen atom from at least one member of the class consisting of trivalent unsaturated hydrocarbon chains which jointly with the nitrogenform a heterocycle, divalent saturated aliphatic chains which jointly with the nitrogen form a heterocycle, and monovalent cycloaliphatic, araliphatic, and aliphatic groups,

impregnating :at least part of the cotton with a 20 solution containing about 10% to about 25% of a compound of the formula nocngn- V wherein R is a group which contains 7 to 14 carmn atoms and is selected from a member of the class consisting of aliphaticiand cycloaliphatichydrocarbon groups 'and aralkyl groups, X1 is a salt-forming anion, and- R 1, R2, and R3 are organic groups selected to satisfy three valences of the nitrogen atom from at least one member of the class consisting of trivalent unsaturated hydrocarbon chains which jointly with the nitrogen form a heterocycle, divalent saturated aliphatic chains which jointly with the nitrogen form a heterocycle, and monovalent cycloaliphatic, araliphatic, and aliphatic groups, heating the impregnated cotton between about 100 C. and about 160 C.. to cause reaction between cotton and quaternary ammonium salt, and subsequently subjecting the treated cotton to'the action of a dye.

. LOUIS H. BOCK.

ALVA L. HOUK. 

